CN1143654A - Covering material for plant growth control - Google Patents
Covering material for plant growth control Download PDFInfo
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- CN1143654A CN1143654A CN96108055A CN96108055A CN1143654A CN 1143654 A CN1143654 A CN 1143654A CN 96108055 A CN96108055 A CN 96108055A CN 96108055 A CN96108055 A CN 96108055A CN 1143654 A CN1143654 A CN 1143654A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
- A01G9/14—Greenhouses
- A01G9/1438—Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/25—Greenhouse technology, e.g. cooling systems therefor
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- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Soil Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Protection Of Plants (AREA)
- Greenhouses (AREA)
- Cultivation Of Plants (AREA)
Abstract
In a covering material comprising a base material containing a colorant, the type and content of the colorant are chosen to provide a photosynthetically effective photon flux (PPF) transmittance of 50% or greater when light is passed through the covering material, and an A value suitable for the purpose of promoting or retarding the growth of plants irradiated with light transmitted by the covering material, the A value being defined by the following equation: A=R/Fr, wherein R is the photon flux of red light in the wavelength range of 600 to 700 nm and Fr is the photon flux of far red light in the wavelength range of 700 to 800 nm.
Description
The present invention relates to the novel covering material of controlling plant growth, it has high utility value to large-scale gardening and private gardening.
The basic purpose of using covering material in extensive gardening and private gardening is the thermosteresis (that is: attenuating ventilation rate) that reduces from the greenhouse inner atmosphere to extraneous air, thereby reach reasonable attemperation environment, regulate the cultivation cycle, shorten the desired cultivation time, increase cultivation number of times or the like purpose.In addition, such covering material has the effect of blocking rain, and then stops agrochemicals and fertilizer loss to the outside, greenhouse, also can allow carbonic acid gas use.
Since basic covering material will be exposed in outside air and the sunlight, wish that so they have a long validity period.And they must have high transmittance.For this purpose, once used glass, plastic plate and film.Especially film has advantage cheap and that can easily be attached and remove.On the other hand, cheese cloth usually uses for the inside, greenhouse that acts on of heat isolation and hot season sunshade.
Therefore, the basic function of the covering material that uses for practical purpose at present is will keep and the controlled temperature environment.
Other function as for covering material, the quick progress of research took place in photic form along with nineteen fifties, the research that comprises the optical property utilization of photic form generation control is carried out energetically in Japan, under farming and forestry and the leader of fishery portion, passed through the time of two more than ten years to nineteen eighty-three., also obtain the result have practical value so far.(agricultural and gardening, 69 volumes, the 9th phase, P986,1994).
At present, the seedling of producing in the seedling production mechanism usually trends towards hypertrophy, is short and small and sturdy seedling but people wish.Short and small seedling can be resisted natural environmental condition (surviving better) under adverse weather, and is effectively to reducing the plant minimum level that lodges also, and then has stoped the loss of crop yield.In flower culture, the value height of the flowering plant of long shoot as cut-flower arranged, and have the ground controlled approach of a large amount of flowers to tend to expect that making basin plants thing.In cultivation of fruit tree, the plant of dwarfing helps the raising of cultivability.And, just sow the inoculation seedling, panel length is that robot prunes required uniformly.Like this, the prolongation growth effect of plant is to their commercial value.Use now with the Chemical Regulation of dwarfing agent or mechanical slow effect (promptly prune and prune), but need a kind of safer method more easily.
On the experiment basis that uses source of artificial light, can recognize routinely, in comprising the luminous environment of a high proportion of far-red light, can promote plant to prolong growth.The increase that this reason supposition is a far-red light has caused the decline (wherein r is the 660nm optical throughput, and fr is the 730nm optical throughput) of r/fr ratio, and the ratio of reduction has changed the photostationary state of phytochrome, and this result is as the signal that promotes that plant prolongs.On the other hand, well-known, plant prolongs also can be blocked in comprising the luminous environment of ruddiness at high proportion., adopt covering material to prove that these facts yet there are no report.For example, the film that is used for controlling UV-light and visible light discloses 117738/ ' 77 at Japanese Patent, 132648/ ' 89, be in the news in 283212/ ' 90 and 170322/ ' 86, but about the influence of far-red light, the relation of r/fr ratio, the short effect or the like that prolongs is not stated.About the film of control far-red light, they also do not report the influence of concrete vegetation type at all.
The present inventor once illustrated, when estimating, designing and selecting source of artificial light to be used for plant growing, from photic form generation angle, not only photosynthetic effective light quantity (for example PPF transmissivity) is important, and the ratio of the light in ruddiness zone and far-red light area light also is important, and then infers that it is that plant is required that the light source of high PPF luminosity factor and controllable ruddiness/far-red light ratio are arranged.And, showed already that when ruddiness/far-red light ratio during as the indicator of Morphology Control in the artificial lighting environment in plant growing, it was only using the wavelength period of the 700-800nm of the wavelength period of 600-700nm of ruddiness (R) and far-red light (Fr).And, they have made four wavelength region may emission-type fluorescent lamp bulbs, they have high PPF luminosity factor and the R/Fr ratio of three levels recording by experiment, they have proved the control effect (Murakami etc. of its prolongation growth, ecotope control, 30 volumes, 4 phases, Pp.135-141,1992).But the considerable instrument of service requirements and the process cost (for example electricity charge) of these source of artificial light.Therefore, present condition needs more cheap technology.
The covering material that the purpose of this invention is to provide a kind of controlling plant growth, it allows to use natural light (daylight), and cheap, and operation easily is fit to practical.
In order to address the above problem, present the investigating further of doing of present inventor found that, changes the R/Fr ratio (R: based on the optical throughput of standard illuminants agent D65 in the 600-700nm wavelength region of the transmitted light that acts on the plant by using covering material; Fr: based on the optical throughput of standard illuminants agent D65), controlling plant growth easily in the wavelength region of 700-800nm.The present invention finds to finish on the basis at this.
Promptly the present invention relates to the covering material of controlling plant growth, it comprises the basic material that contains pigment, it is characterized in that, when light when covering material sees through, covering material has 50% or bigger photosynthetic effective luminous flux (PPF) transmissivity, covering material also has one according to the A value that promotes or delay plant is grown and selected, and the A value is defined by following equation:
A=R/FrR is the ruddiness optical throughput in the 600-700nm wavelength region, and Fr is the far-red light optical throughput in the 700-800nm wavelength region.
And, the invention still further relates to a kind of covering material, when light transmission it the time, it has 50% or bigger photosynthetic effective luminous flux (PPF) transmissivity, also promising promoting growth of plants selected 0.9 of covering material or littler A value or be retardance plant-growth selected 1.3 or bigger A value.
In recent years, rationalizing viewpoint from the plant growing of strong seedling rather than seed from agricultural sees and becomes popular day by day.In seedling is produced, expect suitable control seedling early growth and then increase their commercial value.Covering material of the present invention can make plant-growth be controlled in the cheap and easy-operating mode, so it is very important in seedling early growth mechanism, very valuable.
And if covering material is laid in the plastics room of routine movably according to the present invention, the growth of plant can be easy to be controlled in the scope that is fit to required purpose.
Like this, band leaf vegetables, fruit shape vegetables, root shape vegetables, in the extensive cultivation of various decorative plants and fruit tree, covering material of the present invention from improve the quality, laborsaving viewpoint has very high use value.
Covering material of the present invention comprises and has 0.9 or the covering material of littler A value, so it is as quickening plant-growth, and has 1.3 or the covering material of more A value, so it is as blocking plant-growth.
Among the present invention, by use 600 and 700nm between have maximum absorption pigment, the A value is adjusted to 0.9 or littler.On the other hand,, preferably between 700nm to 800nm, have the pigment of maximum absorption, the A value is adjusted to 1.3 or more by using between 700 to 900nm.
And, in order to reach 50% or bigger PPF transmissivity, use to have height and absorb optionally pigment, promptly in selected wavelength region, show significantly to absorb, but in other wavelength region, show very little absorption.PPF transmissivity used herein and A value are basic calculation with standard illuminants agent D65.From the viewpoint of effect, natural is that the pigment that uses in covering material of the present invention should have gratifying high-durability.
When light transmission, covering material of the present invention can have one 50% or bigger photosynthetic effective luminous flux (PPF) transmissivity and 0.9 or littler A value, or 1.3 or bigger A value.Be to promote growth, A value can preferred 0.3 to 0.9 scope, or grows preferred 1.3 to 3.0 scopes of A value for retardance.Its typical example comprises that (1) comprises the resin film or the resin board of high polymer resin, the pigment that wherein has an above-mentioned performance is disperseed or is dissolved, (2) resin board, sheet glass or resin film, it applies with the coating composition that contains above-mentioned pigment, (3) resin film, resin board or sheet glass, thereon in conjunction with the resin film that contains or apply above-mentioned pigment, (4) resin film, resin board or sheet glass, the help of the tackiness agent by comprising above-mentioned pigment makes it and other resin film resin board or sheet glass combination.
When the A value is adjusted to 0.9 or more hour, the covering material that obtains is as promoting plant-growth.On the other hand, be adjusted to 1.3 or when bigger, the covering material that obtains is fit to the retardance plant-growth when the A value.Be to promote plant-growth, A value more preferably 0.8 or littler, perhaps for blocking plant-growth, A value more preferably 1.4 or littler.Be to promote plant-growth, A value is 0.7 or littler, and perhaps for blocking plant-growth, the A value is 1.5 or more greatly is more preferably scope.
In two kinds of situations, the optical transmission rate should be preferably high as much as possible beyond the wavelength region of being controlled.Specifically, should preferred 50% or more, 65% or more mostly be more preferably scope in photosynthetic effective luminous flux (PPF) transmissivity of 400 to 700nm wavelength regions, be more preferably 70% or more.If it is less than 50%, photosynthesis of plant will be suppressed, and cause having the immature plant of seldom chlorophyllous hypertrophy.
As used herein, the promotion ＂ of term ＂ plant-growth refers to plant height, the length of stem, and the acceleration of panel length or the like prolongs, and follows and quickens to prolong the decline of the nutritive substance of per unit volume (as chlorophyll, VITAMIN and protein) content; The accelerating growth of side shoot; Acceleration is bloomed; Because the results ahead of time that plant-growth is quickened to cause; Increase of initial capacity or the like.On the other hand, the retardance ＂ of term ＂ plant-growth refers to because plant height, stem length, panel length or the like) plant that blocked prolongation caused becomes short and small; Follow dwarfing; The increase of sturdy tree bar per unit volume nutritive substance (as chlorophyll, VITAMIN and protein) content; The retarding of growing of side shoot; Since the slow extension that causes of plant-growth gather in the crops or the like analogue.
As above-mentioned used term ＂ cover ' refer to covering material all faces of plant or at least the light one side of coming in hold the interception of plant.
Terminology used here ＂ light ＂ refers to natural light or from the light of source of artificial light.Though the use of natural light sees it is favourable from the expense angle, the use that the present invention also can be applied to source of artificial light also is a matter of course.And reflected light also can be used.Be plant-growth can by in covering material the inside or the outside place reverberator and control, the reflected light that has like this by the Wavelength distribution of covering material control just shines on the plant.
The used basic material of the present invention preferably comprises the resin that can form flat board or film, and it has high as far as possible transparency.The object lesson of this resin comprises the addition polymer of vinyl compound and vinyl compound, as polyethylene, and polyacrylic acid, polymethyl acrylic acid, polyacrylic ester, polymethacrylate; Polyvinyl acetate, polyacrylonitrile, polyvinyl chloride and fluorinated ethylene propylene; The multipolymer of vinyl compound or fluorochemicals, as polyvinylidene dichloride, poly(vinylidene fluoride).The polyvinylene dintrile, vinylidene fluoride/trifluoro-ethylene copolymer, vinylidene fluoride/TFE copolymer, vinylidene dintrile/vinyl acetate copolymer and vinyl acetate/ethylene copolymer (EVA); Fluorochemicals is as poly-trifluoro-ethylene, tetrafluoroethylene and polyhexafluoropropylene; Polymeric amide such as nylon 6 and nylon 66; Polyimide; Polyurethane; Poly-peptide; Polyester such as polyethylene terephthalate; Polycarbonate; Polyethers such as polyoxymethylene, polyethylene oxide and poly(propylene oxide); Resins, epoxy; Polyvinyl alcohol and polyvinyl butyral acetal.Conventional purpose hardened resin such as polyethylene terephthalate, polycarbonate and polymethylmethacrylate and agricultural soft resin such as polyvinyl chloride, polyvinyl acetate, polyethylene and vinyl acetate/ethylene copolymer (EVA) they are preferred especially.
Being used for adjusting A value to 0.9 or littler pigment should preferably have the pigment of maximum absorption effect between 600 to 700nm, its concrete example comprises, but is not limited only to following pigment:
Preferred pigment comprises the phthalocyanine compound of general formula given below (1) and the naphthoquinone compound of general formula given below (2) or (3), because the weather resistance that they have high absorbing wavelength selectivity to become reconciled.
A wherein
1To A
8In each be respectively hydrogen atom or halogen atom; B
1To B
8In each be respectively hydrogen atom, halogen atom replaces or the unsubstituted alkyl group, replace or unsubstituted alkoxy base, replace or unsubstituted aromatic yl group, replace or unsubstituted aryloxy group, replace or unsubstituted alkylthio group or replacement or unsubstituted arylthio group; M is a divalent metal atom, the trivalent of replacement or tetravalent metal atom or oxygen metal group.
A wherein
11And A
12Each is respectively an amino group, replaces or unsubstituted alkylamino group, or replacement or unsubstituted fragrant amino group; B
11To B
14Each be respectively hydrogen atom, halogen atom replaces or the unsubstituted alkyl group, replaces or unsubstituted alkoxy base, replaces or unsubstituted aromatic yl group, or replacement or unsubstituted aryloxy group.
A wherein
13And A
14In each be respectively amino group, replace or do not replace the alkylamino group, or replace or do not replace fragrant amino group; B
15To B
18In each be respectively hydrogen atom, halogen atom replaces or the unsubstituted alkyl group, replaces or non-substituted alcoxyl group, replaces or the unsubstituting aromatic yl group, or replacement or unsubstituted aryloxy group.
About the phthalocyanine compound of above-mentioned molecular formula (I), by A
1To A
8And B
1To B
8The substituting group group of representative and provide below by the object lesson of the metal of M representative:
The example of halogen atom comprises fluorine, chlorine, bromine and iodine atom.
The example of the alkyl group of replacement or non-replacement comprises the alkyl group of straight chain or branched 1 to 20 carbon atom, as methyl, and ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, 1, the 2-dimethyl propyl, n-hexyl, cyclohexyl, 1,3-dimethylbutyl, 1-sec.-propyl propyl group, 1,2-dimethylbutyl, normal heptane, 1,4-dimethyl amyl group, 2-methyl isophthalic acid-sec.-propyl propyl group, 1-ethyl-3-methyl butyl, n-octyl, 2-ethylhexyl, 3-methyl isophthalic acid-sec.-propyl butyl, 2-methyl isophthalic acid-sec.-propyl, the 1-tertiary butyl-2-methyl-propyl and n-nonyl; Alkoxyalkyl, alcoxyl alkoxyalkyl and alcoxyl alcoxyl alkoxyalkyl group such as methoxyl methyl, methoxyethyl, ethoxyethyl, the third oxygen ethyl, fourth oxygen ethyl, γ-methoxycarbonyl propyl, γ-ethoxy propyl group, methoxy (ethoxy) ethyl, ethoxy ethoxyethyl, the dimethoxy methyl, diethoxy methyl, dimethoxy ethyl and diethoxy ethyl, alkyl group such as chloromethyl that halogen replaces, 2,2,2-three chloroethyls, trifluoromethyl, 2,2,2-three chloroethyls and 1,1,1,3,3,3-hexafluoro-2-propyl group; Alkylamino alkyl, dialkyl aminoalkyl, alkoxycarbonyl alkyl, alkyl amino alkyl carbonyl and alcoxyl alkylsulfonyl alkyl.
The example of replacement or unsubstituted alkoxy grp comprises the alkoxy grp of 1 to 20 carbon atom of straight or branched, as methoxyl group, and oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, isopentyloxy, neopentyl oxygen, 1,2-dimethyl propoxy-, positive hexyloxy, cyclohexyloxy, 1,3-dimethyl butoxy, 1-sec.-propyl propoxy-, 1,2-dimethyl butoxy, positive heptan the oxygen base, 1,4-dimethyl pentyloxy, 2-methyl isophthalic acid-sec.-propyl propoxy-, 1-ethyl-3-methyl butoxy, n-octyloxy, 2-ethyl hexyl oxy, 3-methyl isophthalic acid-sec.-propyl butoxy, 2-methyl isophthalic acid-isopropoxy, the 1-tertiary butyl-2-methyl propoxy-and positive ninth of the ten Heavenly Stems the oxygen base; Alkoxyalkoxy group, alcoxyl alkoxyalkoxy group and alcoxyl alcoxyl alkoxyalkoxy group group are as methoxy methoxy base, methoxyethoxy, the ethoxy oxyethyl group, the third oxygen oxyethyl group fourth oxygen oxyethyl group, γ-methoxy propoxy-, γ-ethoxy propoxy-, the methoxy (ethoxy) oxyethyl group, ethoxy ethoxy oxyethyl group, dimethoxy methoxyl group, diethoxy methoxyl group, the dimethoxy oxyethyl group, diethoxy oxyethyl group and fourth oxygen ethoxy oxyethyl group; Halogenated alkoxy group such as chlorine methoxyl group, 2,2,2-three chloroethoxies, trifluoromethoxy, 2,2,2-three chloroethoxies and 1,1,1,3,3,3-hexafluoro-2-propoxy-, alkylamino alcoxyl and dialkyl amido alkoxy grp such as dimethylamino ethoxy and diethyl amino base oxethyl.
The example of replacement or unsubstituted aromatic yl group comprises phenyl, halogenophenyl (as chloro-phenyl-, dichlorophenyl, bromophenyl, fluorophenyl and iodophenyl), tolyl, xylyl, dish base, ethylbenzene base, methoxyphenyl, phenelyl and pyridyl group.
The example of replacement or unsubstituted aryloxy group comprises phenoxy group, naphthyloxy and alkyl phenoxy group.
The example of replacement or unsubstituted alkylthio group comprises the alkylthio group of straight chain or branched 1 to 20 carbon atom, as methylthio group, and ethylmercapto group, positive rosickyite base, iprotiazem, positive butylthio, the isobutyl sulfenyl, secondary butylthio, uncle's butylthio, positive penta sulfenyl, different the eleventh of the twelve Earthly Branches sulfenyl, new penta sulfenyl, 1,2-dimethyl propylene sulfenyl, just own sulfenyl, the hexamethylene sulfenyl, 1,3-dimethyl butyrate sulfenyl, 1-sec.-propyl rosickyite base, 1,2-dimethyl butyrate sulfenyl, h-sulfenyl in heptan, 1,4-dimethyl-penten sulfenyl 2-methyl isophthalic acid-sec.-propyl rosickyite base, 1-ethyl-3-methyl butylthio, positive hot sulfenyl, the own sulfenyl of 2-ethyl, 3-methyl isophthalic acid-sec.-propyl butylthio, 2-methyl isophthalic acid-iprotiazem base, the 1-tertiary butyl-2-methyl-prop sulfenyl and positive ninth of the ten Heavenly Stems sulfenyl; The alcoxyl alkylthio, alcoxyl alcoxyl alkylthio and alcoxyl alcoxyl alcoxyl alkylthio group such as methoxy methylthio group, methoxy ethylmercapto group, the ethoxy ethylmercapto group, the third oxygen ethylmercapto group, fourth oxygen ethylmercapto group, γ-methoxy rosickyite base, γ-ethoxy rosickyite base, methoxy (ethoxy) ethylmercapto group, ethoxy ethoxy ethylmercapto group, dimethoxy methylthio group, diethoxy methylthio group, dimethoxy ethylmercapto group diethoxy ethylmercapto group, halogenated alkylthio group such as chloromethane sulfenyl, 2,2,2-trichlorine ethylmercapto group, trifluoromethylthio, 2,2,2-trichlorine ethylmercapto group and 1,1,1,3,3,3-hexafluoro-2-rosickyite base, alkylamino alkylthio and dialkyl amido alkylthio group such as dimethylamino ethylmercapto group and diethylamino ethylmercapto group.
The example that replaces or do not replace the arylthio group comprises thiophenyl, naphthalene sulfenyl, 4-methylbenzene sulfenyl, 4-ethylbenzene sulfenyl, 4-propylbenzene sulfenyl, 4-tert.-butylbenzene sulfenyl, 4-anisole sulfenyl, 4-ethoxy thiophenyl, 4-phenalgin sulfenyl, 4-alkane phenalgin sulfenyl, 4-dialkyl amino thiophenyl, 4-phenylamino thiophenyl, 4-phenylbenzene phenalgin sulfenyl, 4-hydroxybenzene sulfenyl, 4-chlorobenzene sulfenyl, 4-bromobenzene sulfenyl, 2-toluene sulfenyl, 2-ethylbenzene sulfenyl, 2-propylbenzene sulfenyl, 2-tert.-butylbenzene sulfenyl, 2-methoxy thiophenyl, 2-ethoxy thiophenyl, 2-phenalgin sulfenyl, 2-alkane phenalgin sulfenyl, 2-dialkylamino thiophenyl, 2-phenylamino thiophenyl, 2-hexichol phenalgin sulfenyl, 2-oxybenzene sulfenyl, 2-chlorobenzene sulfenyl and 2-bromobenzene sulfenyl.
Example by the divalent metal of M representative comprises Cu (II), Zn (II), Fe (II), Co (II), Ni (II), Ru (II), Rh (II), Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Id (II), Hg (II), Pb (II) and Sn (II).
The example of mono-substituted trivalent metal comprises Al-Cl, Al-Br, Al-F, Al-I, Ga-Cl, Ga-F, Ga-I, Ga-Br, In-Cl, In-Br, In-I, In-F, Tl-Cl, Tl-Br, Tl-I, Tl-F, Al-C
6H
5, Al-C
6H
4(CH
3), In-C
6H
5, In-C
6H
4(CH
3), Mn (OH), Mn (OC
6H
5), Mn[OSi (CH
3)
3], Fe-Cl and Ru-Cl.
The example of dibasic tetravalent metal comprises CrCl
2, SiCl
2, SiBr
2, SiF
2, SiI
2, ZrCl
2, GeCl
2, GeBr
2, GeI
2, GeF
2, SnCl
2, SnBr
2, SnF
2, TiCl
2, TiBr
2, TiF
2, Si (OH)
2, Ge (OH)
2, Zr (OH)
2, Mn (OH)
2, Si (OH)
2, TiR
2, CrR
2, SiR
2, SnR
2, GeR
2, (wherein each R is alkyl phenyl or naphthyl or their derivative), Si (OR ')
2, Sn (OR ')
2, Ge (OR ')
2, Ti (OR ')
2, Cr (OR ')
2(wherein each R ' is alkyl, phenyl, naphthyl, trialkyl silica and dialkyl group alcoxyl silyl or their derivative.), Sn (SR ")
2And Ge (SR ")
2(wherein each R " be alkyl, phenyl or naphthyl group or their derivative).
The example of oxygen metal group comprises VO, MnO and TiO.
In these phthalocyanine compounds, central metal M is that those compounds of Cu, Ni, Fe, Mn, Mg, Pd or AlCl are especially preferred.
About having the naphthoquinone compound of top molecular formula (2) and (3), by A
11To A
14And B
11With B
18The object lesson of the substituted radical of representative is provided by following.
The example of halogen atom comprises fluorine, chlorine, bromine and iodine atom.
The example of replacement or unsubstituted alkyl group comprises straight chain or branched alkyl group such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl and neo-pentyl.
The example of replacement or unsubstituting alkoxy group comprises straight chain or branched alkoxy grp such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, isobutoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, isopentyloxy and neopentyl oxygen.
The example of replacement or unsubstituting aromatic yl group comprises phenyl, halogenophenyl (as chloro-phenyl-, dichlorophenyl, bromophenyl, fluorophenyl and iodophenyl), tolyl, xylyl, dish base, ethylbenzene base, methoxyphenyl, phenelyl and pyridyl group.
The example of replacement or non-substituted aryloxy group comprises phenoxy group, naphthyloxy, alkane phenoxy group and alcoxyl phenoxy group group.
Replace or the example of substituted alkyl amino group does not comprise methylamino-, ethylamino, third amino, fourth amino, penta amino, diamyl amino, oneself is amino, heptan amino, hot amino and the ninth of the ten Heavenly Stems amino group.
The example that replaces or do not replace fragrant amino group comprises phenylamino, alkane phenylamino, alcoxyl phenylamino, oxybenzene amino and naphthylamino group.
On the other hand, be used for adjusting A value to 1.3 or bigger pigment should preferably have the maximum absorption effect between 700 to 900nm pigment.Its concrete example but be not limited to this and comprise following pigment:
More preferred pigment comprises the phthalocyanine compound of tool general formula given below (4) and the naphthalene cyanine compound of tool general formula given below (5), because the weather resistance that they have high absorbing wavelength selectivity to become reconciled.
A wherein
21To A
36In each be respectively hydrogen atom, halogen atom, replace or the unsubstituted alkyl group, replace or unsubstituted alkoxy grp, replace or unsubstituted aromatic yl group, replace or unsubstituted aryloxy group, replace or unsubstituted alkylthio group, replace or unsubstituted arylthio group; A
21, A
24, A
25, A
28, A
29, A
32, A
33And A
36In at least four each all be to replace or unsubstituted alkoxy grp, replace or the unsubstituted aryloxy group, replace or unsubstituted alkylthio group, or the arylthio group of replacement or non-replacement; A
21And A
22, A
22And A
23, A
23And A
24, A
25And A
26, A
26And A
27, A
27And A
28, A
29And A
30, A
30And A
31, A
31And A
32, A
33And A
34, A
34And A
35, A
35And A
36Each to can be respectively forming ring as intermediary by oxygen and/or sulphur atom; M is a divalent metal atom, replaces trivalent and tetravalent metal atom, or the oxygen metal group.
About A in the molecular formula (4)
21To A
36Ring form, the fragment that has four substituted radicals at least one (is A
21To A
24, A
25To A
28, A
29To A
32Or A
33To A
36) at least one pair of adjacent substituting group group can form ring.More particularly, to have A
21To A
24Fragment during as typical example, ring forms in any situation that can occur in following four kinds of modes:
(i) has only A
21And A
22Form ring.
(ii) has only A
23And A
24Form ring.
(iii) A
21And A
22Form ring, simultaneously A
23And A
24Form ring.
(iv) has only A
22And A
23Form ring.
Identical rule correspondingly is applicable to the B that will be described later
22To B
43The formation of ring.
B wherein
21To B
44In each be respectively hydrogen atom, halogen atom, replacement or unsubstituted alkyl group replace or unsubstituted alkoxy base, replace or unsubstituted aromatic yl group, replace or the unsubstituted aryloxy group, replace or unsubstituted alkylthio group, replace or unsubstituted arylthio group B
22And B
23, B
23And B
24, B
24And B
25, B
28And B
29, B
29And B
30, B
30And B
31, B
34And B
35, B
35And B
36, B
36And B
37, B
40And B
41, B
41And B
42, B
42And B
43Can form ring by oxygen and/or sulphur atom as intermediary respectively; M is a divalent metal atom, the trivalent of replacement or tetravalent metal atom, or oxygen metal group.
About the phthalocyanine compound of the above-mentioned molecular formula of tool (4) and the naphthalene cyanine compound of the above-mentioned molecular formula of tool (5), by A
21To A
36And B
21To B
44Halogen atom, replacement or the non-substituted alkyl group of representative, replace or non-substituted alcoxyl group, replace or non-substituted aryl group, replace or non-substituted aryloxy group replaces or unsubstituted alkylthio group group, replace or do not replace the object lesson of arylthio group and above-named by B
1To B
8The substituted radical of representative is the same.By the divalent metal atom of M representative, the object lesson of the trivalent of replacement or tetravalent metal atom and oxygen metal group is with above-named the same similarly.
Work as A
21And A
22, A
22And A
23, A
23And A
24, A
25And A
26, A
26And A
27, A
27And A
28, A
29And A
30, A
30And A
31, A
31And A
32, A
33And A
34, A
34And A
35, A
35And A
36, B
22And B
23, B
23And B
24, B
24And B
25, B
28And B
29, B
29And B
30, B
30And B
31, B
34And B
35, B
35And B
36, B
36And B
37, B
40And B
41, B
41And B
42, B
42And B
43Each when forming ring as intermediary by oxygen and/or sulphur, so the substituent object lesson that forms is as follows:
R wherein
1, R
2And R
3In each be the aryl of replacement or unsubstituted alkyl or replacement or non-replacement, X
1And X
2In each be respectively Sauerstoffatom or sulphur atom, n is 1 to 4 integer.
In above-mentioned phthalocyanine compound, all A
21, A
24, A
25, A
28, A
29, A
32, A
33, A
36Be to replace or those compounds of unsubstituting alkoxy group are especially preferred, and central metal M is Cu, Pd, AlCl, those compounds of TiO or VO are more preferred.
In above-mentioned naphthalene cyanine compound, all B
21, B
26, B
27, B
32, B
33, B
38, B
39, B
44Those compounds that are hydrogen atom are especially preferred, and central metal M is Cu, Pd, and AlCl, those compounds of TiO or VO are more preferred.
Covering material of the present invention is with resin board, film, glass or similarly form make then processing as requested.Though for the method for using above-mentioned pigment manufacturing to be used for the covering material of plant-growth control special restriction is not set, following three methods can be used according to the method for embodiment.They comprise:
(1) a kind of comprising resin is mixed with pigment, the mixture that hot-cast obtains is to form the method for resin board or film.
(2) prepare the coating composition that contains pigment a kind of comprising, it is applied to the method for transparent resin plate, transparent film or transparency glass plate.
(3) a kind of tackiness agent manufacturing laminated resin plate, the multilayer resin film that contains pigment by use, method of laminated glass or analogue of comprising.
Method (1) comprises the mixture that resin mixes with pigment and hot-cast obtains, and wherein, basic resin should preferably can form as far as possible the plate of high-clarity or the resin of film.Its concrete example comprises the above-named various resins that are used as basic material in the present invention.
Though treatment temp, film formation condition or the like can be according to the basic resin that is adopted changes more or less, this method is usually following carries out: pigment joins in the Powdered or globular basic resin, and mixture heating up is to 150-350 ℃ of fusion.This melt can be cast resin board or be formed film with extrusion machine.Interchangeable another kind of method be by the extruding melt form thick film then with stretch ratio 2-5 at 30-120 ℃ of single shaft or biaxial stretch-formed thick film, and form the film of 10-200 μ m thickness.And, the melt casting, rolling processing and other technology also may adopt.At mix stages, the additive for resin casting purpose adopts usually as ultraviolet absorbers and softening agent, also may join in the basic resin.Though according to the thickness of the rosin products that will make, the specific absorption of needs, PPF transmissivity of needs or the like, the amount of pigment of interpolation may change, it is usually in the scope of 1PPm to 1%.
Method (2) comprises that preparation contains the coating composition of pigment, and it is applied to basic material, and wherein, coating composition may make by dissolving pigment in binder resin and organic solvent.Interchangeable another kind of method is by directly in acrylic emulsions, the water-soluble pigment of dissolving in water base urethane coating or the analogue, perhaps pass through the insoluble pigment of grinding water to several microns or littler particle size, it is dispersed in acrylic emulsions, water base urethane coating or the analogue then, and makes water-based coating composition.In the previous case, binder resin is selected from aliphatic ester resin, acrylic resin, melmac usually, urethane resin, the aromatic ester resin, polycarbonate resin, aliphatic polyolefin resin, the fragrance polyolefin resin, polyvinyl resin, polyvinyl alcohol resin, modified polyethylene resin (as PVB and EVA) and their copolymer resin.
Solvent can be from halohydrocarbon, alcohol, and ketone, ester, the fat hydrocarbon is selected in aromatic hydrocarbons, ether and their mixture.
Though according to coat-thickness, the optical density that needs, PPF transmittance that needs or the like, pigment concentration may change, and it is usually based on the weight of binder resin, in the scope of 0.1 to 30% (by weight).
Based on the gross weight of coating composition, binder resin concentration is usually in 1 to 50% scope by weight.In the later case, in colourless ACRYLIC EMULSION, the pigment (50 to 500nm particle size is arranged) that dissolving pigment or dispersion are ground in water base urethane coating or the analogue can prepare water-based coating composition equally.This coating composition can further be included in the additive that often uses in the coating composition, as uv-absorbing agent and oxidation inhibitor.So, use bar-shaped coating machine, blade coating machine, rotation coating machine, reverse coating machine, template coating machine, Bracewell coater or analogue, the coating composition of aforesaid way preparation is applied to transparent resin film, transparent resin plate or transparent glass, can be made the covering material that is used for plant-growth control.For the protection coated surfaces, can form protective layer at coated surfaces, perhaps transparent resin plate, transparent resin film or analogue can be laminated to coated surfaces and form thin layer.And cast films also can be used in this method.
Method (3) comprises uses the tackiness agent that contains pigment to make laminated resin plate, multilayer resin film, laminated glass or analogue, wherein can use the common siloxanes, urethane and the acryloid cement that use with resin, can use the well-known clear binder that in laminated glass, uses, as polyvinyl butyral (PVB) and ethylene-vinyl yl acetate (EVA) tackiness agent.
Under the help of the tackiness agent that contains 0.1 to 30% pigment, by resin board is combined, resin film and resin board, resin board and sheet glass, resin film, resin film and sheet glass, sheet glass are combined, and the covering material that is used for plant-growth control can be made.Interchangeable another kind of method is that such covering material also can be made by hot binding.
Although the vegetation type that covering material of the present invention covered is not provided with special restriction, such plant comprises for example vegetables: Curcurbitaceae, Solanaceae, pulse family, the Rosaceae, Cruciferae, composite family, umbelliferae, Chenopodiaceae, Gramineae, Malvaceae, Araeceae, Labiatae, Zingiber, Nymphaeceae and Araliaceae; Flowering plant (comprising cut-flower and potted flower): composite family, the Rosaceae, Araeceae, Caryophyllaceae, Cruciferae, lumbaginaceae, Gentianaceae, scrophulariaceae, pulse family, Iridaceae, Solanaceae, Amaryllidaceae, the orchid family, Cornaceae, Rubiaceae, Salicaceae, Ericaceae, Oleaceae, Magnoliaceae, Primulaceae, Begoniaceae, Labiatae,
Ox seedling section, Crassulaceae, Ranunculaceae, Gesneriaceae and Cactaceae, Polypodiales and Araliaceae, Moraceae, Commelianaceae, Bromelia family, Marantaceae, Euphorbiaceae, piperaceae, Saxifragaceae, root of Redsepal Eveningprimrose section, Malvaceae, Myrtaceae, Theaceae and Nyctaginaceae; Fruit tree: the Rosaceae, Vitaceae, Moraceae, Ebenaceae, Oenothera, Ericaceae, Lardizabalaceae, Actinidiaceae, Passifloraceae, Rutaceae, Anacardiaceae, Bromelia family and Myrtaceae; Also has algae.
Their concrete example comprises Sunflower Receptacle (Helianthus annuus), cucumber (Cucumis sativis), lettuce (Lactuca sativa), cabbage (Brassicaoleracea), sesame (Sesamum indicum), green peppers (Capsicum annuum), eggplant (Solanum melongena), rape (Brassica campestris), trifolium (Cryptotaenia canadensis), spinach (Spinacia oleracea), pumpkin (Cucurbita moschata), watermelon (Citrullus battich), muskmelon (Cucumismels), Doliclos lablab, wild cabbage, strawberry (Fragaria chiloensis), mandarin orange (Citrus unshiu), pears (Pyrus serotina), grape (Vitis vinifera), one chrysanthemum (Chrysanthemum morifolium), onion (Allium cepa), tomato (Lycopersicon esculentum), Common Snapdragon (Antirrhinum majus), carnation (Dianthus caryophyllus), Herba lamii barbati (Lamium amplexicaule), rose (Rosa sp.), Statice, violet, prairie gentian belongs to, orchid, Cyclamen persicum (Cyclamen persicum), impatiens, Flower of Aztec Marigold, Salvia, staggerweed, Root of Rocket Consolida, didiscus, A Miqin (Ammimajus), lily (Lilium sp.), freesia (Freesia reflacta), Jris, Flower of Beltleaf Primrose (Primula sieboldi), Flower of Evans Begonia, crowndaisy chrysanthemum, Petasites officinalis Moench (Petasites japonicus), garlic sprouts (Allium tuberosum), shallot (Allium tuberosum), asparagus fern (Asparagus officinalis), celery (Apium gravelens), radish (Raphanus sativus), pea (Pisumsativum) and loquat (Eriobotryajaponica).
Suppose face that can the be enough such covering material of covering material of the present invention is all with plant or at least the one side that enters of light hold, covering material of the present invention should be provided with special restriction in the method for gardening mechanism.Its typical example comprises by using the resin board that obtains in the aforesaid way or glass to build up glass or plastics room and then being suitable for the method for controlling plant growth, use is used for the outer cover in tubulature room and plastics room and/or the method for the resin film in the inner shirt, use is used for the method for the resin film in room, flint road, uses the method as the resin film of ground coating film.In the situation of fruit tree, not only each tree can hold with covering material fully, and its side shoot of while can cover wherein respectively.
In private gardening, according to the suitable method of those methods that is applied to gardening mechanism, covering material of the present invention can use suitably, is for example made the method for the covering potted plant of miniature dimensions box by resin board.
When covering materials more according to the present invention carry out for the growth of all kinds seedling test, to compare with the situation of the plant that is exposed to natural light, the growth of the plant that is obtained is controlled significantly.
Embodiment
The present invention further specifies by following Example.These examples are not to be intended to limit the scope of the invention.
In the following Example, the degree of growth and retarded growth is calculated based on plant height.Embodiment 1:
100000 parts of 4.2 parts of the phthalocyanine pigments of formula (6) representative and polymethylmethacrylates be at 280 ℃ of mixed meltings, and the miscellany that obtains extruding mold forms has the thick and 1 meter wide colouring resin plate of 2.5mm.When measuring the photosynthetic effective luminous flux of this resin board (PPF) transmissivity and A value, finding that they are respectively 73.3% and 0.58 (based on standard illuminants agent D65) with spectrophotometer (UV-3100 is made by Shimazu Seisakusho K.K.).Use this resin board, make have the 650mm height, 1750mm is wide, 850mm is dark growth cell.In the cultivation below, this growth room places the open air, uses air propeller with 15.2m
3Internal temperature will be equal to outside temperature to such an extent as to the speed of/min is ventilated.The Sunflower Receptacle seedling that the about 8cm of seven strains is high is positioned over above-mentioned growth room, cultivated 10 days, and the result, they grow into high plant, long 18.7 ± 0.5cm between average plant height 26.3 ± 0.7cm, the long 22.1 ± 0.7cm of stem, first segment.
For relatively, cultivate again under the identical condition.It uses with the covering of cheese cloth in the growth room of making except the resin board that does not contain pigment, to such an extent as to provided photosynthetic effective luminous flux (PPF) transmissivity 73.0% (1.05 A values).The average plant height 17.6 ± 0.7cm of plant that obtains like this, the long 14.4 ± 0.8cm of stem, long 10.6 ± 0.6cm between first segment.So can confirm, with the resin board that has subequal PPF transmissivity but do not contain pigment relatively, sunflower plants growth (prolongation) degree of using aforementioned covering material with A value of 0.58 to reach is 1.5 times of the resin board that compares with it.
And when 63 ℃ the above-mentioned colouring resin plate of irradiation carried out the test of photoresistance power in 300 hours down, PPF transmissivity of its demonstration 74.0% and 0.59 A value showed that those numeric ratios before the test of these values and photoresistance more almost do not have variation with carbon arc lamp.Embodiment 2:
Same way as among colouring resin plate such as the embodiment 1 forms, except that 4.0 parts of pigment that replace in the example 1 of pigment of use formula (7) representative.This resin has the A value of photosynthetic effective luminous flux (PPF) transmissivity 73.2% and 0.65.Use this resin board, the Sunflower Receptacle seedling is with cultivating as the same way as in the example 1 fully.As a result, they grow into high plant, its average plant height 25.1 ± 0.7cm, the long 21.5 ± 0.6cm of stem, long 17.8 ± 0.6cm between first segment.So can confirm, the degree of the sunflower plants growth (prolongation) that reaches with the above-mentioned covering material with 0.65A value is 1.4 times of comparative resin plate among the embodiment 1 that compares with it.
Embodiment 3
2.0 parts of the pigment of formula (8) representative are dissolved in 1000 parts of the polyvinyl butyral resins in 180 ℃.Use the form film machine, this mixture forms colored film, and 3m is wide, and 0.2mm is thick.Then, insert this film between the thick two active sheet glass of tool 3mm, what obtain is combined in 140 ℃, and 13 normal atmosphere press down 20 minutes to form laminated glass.This laminated glass has 73.1% photosynthetic effective luminous flux (PPF) transmissivity and 0.60 A value.Use this resin board, make 650mm height, 650mm is wide and 650mm is dark growth room.When the similarity condition of three strain Sunflower Receptacle seedlings such as example 1 was cultivated down, they grew into high plant, long 17.9 ± 0.2cm between its average plant height 25.7 ± 0.4cm, the long 22.2 ± 0.3cm of stem, first segment.So can confirm, sunflower plants growth (prolongation) degree that reaches with the aforementioned covering material with A value of 0.60 is 1.5 times of comparative resin plate among the embodiment 1 that compares with it.
Embodiment 4
The mixture of 1.0 parts of phthalocyanine pigments among the embodiment 1 and 1000 parts in the vinylchlorid that is used for agricultural is 180 ℃ of rolling processing, to form the thick colouring resin film of tool 100 μ m.This resin film has the A value of photosynthetic effective luminous flux (PPF) transmissivity 72.8% and 0.67.Use this resin film, make 650mm height, 1750mm is wide and 850mm is dark growth room.Cultivating sunflower seedling under the same terms in as embodiment 1, they grow into high plant, long 17.5 ± 0.3cm between its average plant height 24.2 ± 0.5cm, the long 20.8 ± 0.4cm of stem and first segment.So can confirm usefulness, Sunflower Receptacle plant strain growth that the aforementioned covering material of tool 0.67A value reaches promotes that (prolongation) degree is 1.4 times of comparative resin plate among the embodiment 1 that compares with it.Embodiment 5
The liquid of being made up of with 3: 7 ratio Yuban SE-60 (being made by Mitsui Toatsu chemical company) and Almatex748-5M (being made by Mitsui Toatsu chemical company) mixes (being mixed with the phthalocyanine pigment in 1% example 2 in the toluene) with toluene with 2: 1 ratio.The mixture that obtains was applied to have the thick pet film of 75 μ m, 130 ℃ of oven dry 15 minutes.Film has 73.2% photosynthetic effective luminous flux (PPF) transmissivity and 0.55 A value.When with as during the same manner cultivating sunflower seedling of example 1, they grow into high plant, its average plant height 26.9 ± 0.8cm, stem are grown long 19.4 ± 0.5cm between 22.0 ± 0.6cm, first segment.So can confirm, growth (prolongation) degree that the aforementioned covering material of apparatus 0.55A value reaches is 1.5 times of comparative resin plate among the embodiment 1 that compares with it.Embodiment 6
Phthalocyanine green is ground into particle diameter 0.2 μ m or littler, and preparation contains the vinylformic acid emulsion coating composition of 1% (weight meter) this phthalocyanine green.This coating composition is applied to the vinyl chloride film of agriculture usefulness.The colouring resin film that obtains has the A value of photosynthetic effective luminous flux (PPF) transmissivity 69.3% and 0.66.When the same way as cultivating sunflower seedling of using as example 1, they grow into high plant, long 16.9 ± 0.3cm between its average plant height 24.8 ± 0.7cm, the long 19.7 ± 0.5cm of stem, first segment.Embodiment 7
Phthalocyanine blue grinds to form particle diameter 0.2 μ m or littler, is prepared into the vinylformic acid emulsion coating composition that contains 1% (weight meter) this phthalocyanine blue.This coating composition is applicable to the ethene chlorine film of agriculture usefulness.The colouring resin film that obtains has the A value of photosynthetic useful photon flow (PPF) transmissivity 70.5% and 0.69.When using as the same manner cultivating sunflower seedling among the embodiment 1, they grow into high plant, long 16.7 ± 0.4cm between its average plant height 23.8 ± 0.6cm, the long 18.7 ± 0.6cm of stem, first segment.Embodiment 8
The cucumber seedling that the about 6cm of seven strains is high be placed on make by the colouring resin plate and in the growth room that embodiment 1 uses, cultivated 9 days.As a result, they grow into high plant, long 6.1 ± 0.5cm between its average plant height 29.4 ± 1.0cm, the long 19.5 ± 0.5cm of stem, first segment.
For relatively, under identical condition, cultivate again, except using the resin board that do not comprise pigment (92.2% PPF transmissivity and 1.05 A value are arranged).The average plant height 22.1 ± 1.4cm of the plant of Huo Deing, stem are grown long 2.9 ± 0.2cm between 11.5 ± 1.2cm, first segment like this.So can confirm, the cucumber growth promotion degree that the covering material of apparatus 0.58A value reaches is 1.3 times of the unpigmented resin board that compares with it.Embodiment 9
With the colouring resin plate that forms as mode identical among the embodiment 1, except 4.0 parts of pigment that replace among the embodiment 1 of naphthoquinones pigment of use formula (9) representative.This resin board has the A value of photosynthetic effective luminous flux (PPF) transmissivity 73.3% and 0.71.Use this resin board, use as the identical mode cultivating sunflower seed seedling among the embodiment 1.As a result, they grow into high plant, long 16.5 ± 0.5cm between its average plant height 23.5 ± 0.7cm, the long 20.0 ± 0.6cm of stem, first segment.So can confirm, Sunflower Receptacle plant strain growth that the covering material of apparatus 0.71A value reaches promotes that (prolongation) degree is 1.3 times of comparative resin plate among the embodiment 1 that compares with it.
Embodiment 10
With being formed with the chromoresin plate, except 4.0 parts of pigment that replace in the example 1 of pigment of use formula (10) representative as the same way as among the embodiment 1.This resin board has the A value of photosynthetic effective luminous flux (PPF) transmissivity 73.2% and 0.69.Use this resin board, with identical mode cultivating sunflower seedling as embodiment 1.As a result, they grow into high plant, long 16.8 ± 0.6cm between its average plant height 24.1 ± 0.7cm, the long 20.5 ± 0.6cm of stem, first segment.So can confirm, the Sunflower Receptacle plant strain growth promotion degree that the above-mentioned covering material of the A value of apparatus 0.69 reaches is 1.4 times of comparative resin plate of the embodiment 1 that compares with it.
Embodiment 11
The colouring resin that the 100 μ m that form with the same way as embodiment 4 are thick is thin, except 1.0 parts of pigment that replace among the embodiment 4 of pigment of use formula (11) representative.This resin has the A value of photosynthetic effective luminous flux (PPF) transmissivity 72.8% and 0.75.Use this resin molding, with same way as cultivating sunflower seedling as example 4.As a result, they grow into high plant, long 15.5 ± 0.3cm between its average plant height 23.2 ± 0.4cm, the long 18.8 ± 0.4cm of stem, first segment.So can confirm, Sunflower Receptacle plant strain growth that the above-mentioned covering material of apparatus 0.75A value reaches promotes that (prolongation) degree is 1.3 times of comparative resin plate among the embodiment 1 that compares with it.
Embodiment 12
The seven strain cucumber seedlings that the about 6cm of seven strains is high are positioned in the growth room that is made and used in embodiment 9 by the colouring resin plate, cultivate 9 days.Long 4.9 ± 0.5cm between the average plant height 26.4 ± 1.2cm of the plant that obtains like this, the long 16.5 ± 0.5cm of stem, first segment.So can confirm, the cucumber plant growth degree that the covering material of apparatus 0.71A value reaches is 1.2 times of comparative resin plate among the embodiment 8 that compares with it.Embodiment 13
Be formed with the chromoresin plate with the same manner, except using 4.2 parts of pigment that replace among the embodiment 1 of phthalocyanine pigment by formula (12) representative as embodiment 1.This resin board has photosynthetic useful photon flow (PPF) transmissivity 76.3% and 2.19 A value is arranged.Use this resin board, with identical mode cultivating sunflower seedling as embodiment 1.As a result, the short strong plant of acquisition, long 5.4 ± 0.4cm between average plant height 10.8 ± 0.8cm, the long 8.1 ± 0.4cm of stem, first segment.
For relatively, under identical condition, test again, except using it, down to having provided photosynthetic effective luminous flux (PPF) transmissivity 76.0% (with 1.05 A value) by holding the resin board that does not contain pigment with cheese cloth.The plant of Huo Deing like this, long 10.5 ± 0.6cm between average plant height 17.5 ± 0.7cm, the long 14.3 ± 0.8cm of stem, first segment.So can confirm, the Sunflower Receptacle plant strain growth retarding degree that the above-mentioned covering material of apparatus 2.19A value reaches is nearly equal PPF transmissivity is arranged but not conforming to 0.6 times of pigmental resin plate of comparing with it.
And, when by with carbon arc lamp when 63 ℃ of irradiation above-mentioned colouring resin plate methods of 300 hours are carried out the photoresistance test, it shows 77.3% PPF transmissivity, 2.09 A value, and those numeric ratios before showing these numerical value and testting at photoresistance more almost do not have variation.Embodiment 14:
Be formed with the chromoresin plate with same way as, except using 4.0 parts of pigment that replace among the embodiment 1 of pigment by formula (13) representative as embodiment 1.This resin board has the A value of photosynthetic effective luminous flux (PPF) transmissivity 76.2% and 1.99.Use this resin board, with identical mode cultivating sunflower seed as embodiment 13.As a result, the short strong plant that obtains, long 5.4 ± 0.4cm between average plant height 11.1 ± 0.7cm, the long 8.8 ± 0.4cm of stem, first segment.So can confirm, the slow degree of Sunflower Receptacle plant strain growth that the above-mentioned covering material of apparatus 1.99A value reaches is 0.6 times of comparative resin plate of the embodiment 13 that compares with it.
Embodiment 15:
Form laminated glass with same way as, except using 2.0 parts of pigment that replace among the embodiment 3 of pigment by formula (14) representative as embodiment 3.This laminated glass has the A value of photosynthetic useful photon flow (PPF) transmissivity 78.9% and 1.60.When the identical mode cultivating sunflower kind period of the day from 11 p.m. to 1 a.m of using as embodiment 3, the plant of acquisition, long 6.4 ± 0.2cm between average plant height 13.2 ± 0.4cm, the long 9.6 ± 0.3cm of stem, first segment.
For relatively, under identical condition, cultivate again, except not conforming to pigment and using by holding it, so that provided photosynthetic effective luminous flux (PPF) transmissivity 78.8% with cheese cloth in order to compare the resin board that in embodiment 1, uses.(with 1.05 A value).Long 10.2 ± 0.6cm between the average plant height 17.1 ± 0.7cm of the plant that obtains like this, the long 13.5 ± 0.4cm of stem, first segment.So can confirm, the retarded growth degree that the Sunflower Receptacle strain that the aforementioned covering material of the A value of apparatus 1.60 reaches is planted is nearly equal PPF transmissivity is arranged but not conforming to 0.8 times of resin board of pigment of comparing with it.Embodiment 16
With forming the thick colouring resin film of 100 μ m, except using 1.0 parts of pigment that replace among the embodiment 4 of phthalocyanine pigment by formula (15) representative as embodiment 4 identical modes.This resin film has 76.0% photosynthetic effective luminous flux (PPF) transmissivity and 1.49 A value.Use this resin film, use as the identical mode cultivating sunflower seedling among the embodiment 4.As a result, the short strong plant of acquisition, long 6.7 ± 0.3cm between average plant height 13.2 ± 0.5cm, the long 9.8 ± 0.4cm of stem, first segment.So can confirm, the Sunflower Receptacle plant strain growth retarding degree that the above-mentioned covering material of the A value of apparatus 1.49 reaches is 0.8 times of comparative resin plate of the embodiment 13 that compares with it.
Embodiment 17
With forming coating film, except using by the pigment among the pigment replacement embodiment 5 of formula (16) representative as the same way as among the embodiment 5.This film has 76.2% photosynthetic effective luminous flux (PPF) transmissivity and 1.50 A value.When using as the identical mode cultivating sunflower seedling among the embodiment 5 long 6.4 ± 0.3cm between the average plant height 13.9 ± 0.4cm of the short strong plant of acquisition, the long 10.0 ± 0.5cm of stem, first segment.So can confirm, the Sunflower Receptacle plant strain growth retarding degree that reaches with the above-mentioned covering material with 1.50A value is 0.8 times of correlated resin board among the embodiment 13 that compares with it.
Embodiment 18:
Form by the miscellany of 1000 parts of 4.0 parts of the naphthalene cyanine pigments of formula (17) representative and polyethylene terephthalates fusion and extrusion molding 300 ℃ the time and to have the thick film of 100 μ m.Then, this film is obtained to have the thick colouring resin film of 25 μ m by two-way stretch.This film has 77.3% photosynthetic effective luminous flux (PPF) transmissivity and 2.00 A value is arranged.When using as the identical mode cultivating sunflower seedling among the embodiment 13 the short strong plant of acquisition, long 5.8 ± 0.4cm between average plant height 11.9 ± 0.6cm, the long 9.5 ± 0.5cm of stem, first segment.So can confirm, the daytime certain herbaceous plants with big flowers plant strain growth retarding degree that the above-mentioned covering material of apparatus 2.00A value reaches is 0.7 times of comparative resin plate among the embodiment 13 that compares with it.
Embodiment 19:
Naphthalene cyanine pigment by formula (18) representative grinds to form particle diameter 0.2 μ m or littler, and preparation contains the vinylformic acid emulsion coating composition of 1% this naphthalene cyanine pigment (by weight).This coating composition is applied to agricultural vinyl chloride film.The colouring resin film that obtains has the A value of photosynthetic effective luminous flux (PPF) transmissivity 70.3% and 1.70.When with as the identical mode cultivating sunflower seedling among the embodiment 13, obtain short strong plant, long 5.9 ± 0.3cm between average plant height 12.0 ± 0.7cm, the long 9.7 ± 0.5cm of stem, first segment.
Embodiment 20:
The seven strain cucumber seedlings that the about 6cm of seven strains is high are positioned over the growth room that is made and used by the colouring resin plate in embodiment 13, cultivated 9 days.The average plant height 12.4 ± 1.0cm of the plant of Huo Deing, stem are grown long 1.5 ± 0.5cm between 6.5 ± 0.5cm, first segment like this.So can confirm, the cucumber plant retarded growth degree that reaches with the covering material with 2.19A value is 0.6 times of comparative resin plate among the embodiment 8 that compares with it.Embodiment 21:
Use twin screw extruder machine, 1.5 parts of naphthalene cyanine pigments and polyethylene (V5993 among the embodiment 19, make by Mitsui Dupont company limited) 1000 parts mixed at 200 ℃, form piller, use the single screw extruder that is equipped with T shape mould then, these piller fusion extrusions form has the thick film of 100 μ m.This film has 75.2% photosynthetic effective luminous flux (PPF) transmissivity, 1.53 A value.Cultivate daytime certain herbaceous plants with big flowers seedling when using as the identical mode among the embodiment 4, the short strong plant of acquisition, long 6.6 ± 0.4cm between average plant height 13.2 ± 0.6cm, the long 9.6 ± 0.3cm of stem, first segment.So can confirm, the Sunflower Receptacle plant strain growth retarding degree that the above-mentioned covering material of apparatus 1.53A value reaches is 0.8 times of comparative resin plate among the embodiment 1 that compares with it.Embodiment 22:
With the growth test of having carried out other vegetation type as the same manner among the embodiment 1.What obtain like this results are shown in table 1.
Table 1
Zero: the growth degree is 1.3 or bigger △: the growth degree from 1.1 to less than 1.3 embodiment 23
| Vegetation type | Effect | Vegetation type | Effect | Vegetation type | Effect |
| Lettuce | ??○ | Mandarin orange | ??○ | Prairie gentian | ??○ |
| Cabbage | ??○ | Pears | ??○ | Orchid | ??○ |
| Sesame | ??○ | Grape | ??△ | Cyclamen persicum | ??○ |
| Green peppers | ??○ | Chrysanthemum | ??○ | Flower of Garden Balsam | ??○ |
| Eggplant | ??△ | Onion | ??△ | Mary bush | ??○ |
| Rape | ??△ | Tomato | ??△ | Salvia japonica Thunb. | ??○ |
| Trifolium | ??△ | Common Snapdragon | ??○ | Herba Limonii Gmelinii | ??○ |
| Spinach | ??○ | Carnation | ??△ | Delphinium grandiflorum | ??○ |
| Pumpkin | ??○ | Herba lamii barbati | ??○ | Root of Rocket Consolida | ??○ |
| Watermelon | ??○ | Rose | ??○ | ?didiscus | ??○ |
| Muskmelon | ??○ | A Miqin | ??○ | ||
| Strawberry | ??○ | Violet | ??△ |
With the retarded growth test of carrying out other vegetation type as the same way as of embodiment 13.What obtain like this results are shown in table 2.
Table 2
Zero: the retarded growth degree is 0.7 or minimum △: the retarded growth degree from 0.9 to greater than 0.7.Comparing embodiment 1
| Vegetation type | Effect | Vegetation type | Effect | Vegetation type | Effect |
| Lettuce | ??○ | Mandarin orange | ??○ | Prairie gentian | ??○ |
| Cabbage | ??○ | Pears | ??○ | Orchid | ??○ |
| Sesame | ??○ | Grape | ??△ | Cyclamen persicum | ??○ |
| Green peppers | ??○ | Chrysanthemum | ??○ | Flower of Garden Balsam | ??○ |
| Eggplant | ??△ | Onion | ??△ | Mary bush | ??○ |
| Rape | ??△ | Tomato | ??△ | Salvia japonica Thunb. | ??○ |
| Trifolium | ??△ | Common Snapdragon | ??○ | Herba Limonii Gmelinii | ??○ |
| Spinach | ??○ | Carnation | ??△ | Delphinium grandiflorum | ??○ |
| Pumpkin | ??○ | Herba lamii barbati | ??○ | Root of Rocket Consolida | ??○ |
| Watermelon | ??○ | Rose | ??○ | ?didiscus | ??○ |
| Muskmelon | ??○ | A Miqin | ??○ | ||
| Strawberry | ??○ | Violet | ??○ |
With experimentizing as identical condition among the embodiment 1, except make with the resin board that does not contain pigment and as the growth room that uses among the embodiment 1 hold it with cheese cloth and use, down to having provided photosynthetic effective luminous flux (PPF) transmissivity 20.0% (1.05 A values).As a result, the jejune plant of acquisition has only a small amount of chlorophyll.
Claims (10)
1. the covering material that is used for plant-growth control that comprises the basic material that contains pigment, it is characterized in that, when light passes through, cover material and having 50% or more photosynthetic effective luminous flux (PPF) transmissivity, and the A value in order to promote or block that plant-growth is selected, the A value is defined by following equation:
A=R/FrR is the ruddiness optical throughput in the 600-700nm wavelength region, and Fr is the far-red light optical throughput in the 700-800nm wavelength region.
2. as the desired covering material that is used for plant-growth control in the claim 1, when light by the time, it have 50% or bigger photosynthetic effective luminous flux (PPF) transmissivity, 0.9 or littler A value so that covering material is fit to the promotion plant-growth.
3. as the desired covering material that is used for plant-growth control in the claim 2, the phthalocyanine compound that contains at least a following general formula (1), and when light by the time, it has one 50% or bigger photosynthetic effective luminous flux (PPF) transmissivity, 0.9 or littler A value.
A wherein
1To A
8In each be respectively hydrogen atom or halogen atom; B
1To B
8In each be respectively hydrogen atom, halogen atom replaces or the unsubstituted alkyl group, replace or unsubstituted alkoxy base, replace or unsubstituted aromatic yl group, replace or unsubstituted aryloxy group, replace or replacement of unsubstituted alkylthio group or unsubstituted arylthio group; M is a divalent metal atom, the trivalent of replacement or tetravalent metal atom or oxygen metal group.
4. as the desired covering material that is used for plant-growth control in the claim 2, the naphthoquinone compound that contains at least a following general formula (2) or (3), when light by the time, it has 50% or bigger photosynthetic effective luminous flux (PPF) transmissivity, 0.9 or littler A value.
A
11And A
12Each is respectively an amine groups, replaces or unsubstituted alkylamino group, or replacement or unsubstituted fragrant amine groups; B
11To B
14Each be respectively hydrogen atom, halogen atom replaces or unsubstituted alkyl, replaces or unsubstituted alkoxy base, replaces or unsubstituted aryl, or replacement or unsubstituted aryloxy.
A wherein
13And A
14In each be respectively amino, replace or do not replace alkylamino, or replace or to replace virtue amino; B
15To B
18In each be respectively hydrogen atom, halogen atom replaces or unsubstituted alkyl, replaces or the alkoxyl group of non-replacement, replaces or unsubstituted aryl, or replacement or unsubstituted aryloxy.
5. as the desired covering material that is used for plant-growth control in the claim 3, wherein the M in the phthalocyanine compound of general formula (1) is Cu, Ni, Fe, Mn, Mg, Pd or AlCl.
6. as the desired covering material that is used for plant-growth control in the claim 1, when light by the time, it has 50% or bigger photosynthetic effective luminous flux (PPF) transmissivity, 1.3 or bigger A value, to such an extent as to covering material is fit to block plant-growth.
7. as the desired covering material that is used for plant-growth control in the claim 6, contain the phthalocyanine compound of at least a following general formula (4) and the naphthalene cyanine compound of following general formula (5), when light passes through, it has one 50% or bigger photosynthetic effective luminous flux (PPF) transmissivity, and 1.3 or bigger A value.
A wherein
21To A
36In each be respectively hydrogen atom, halogen atom, replace or the unsubstituted alkyl group, replace or unsubstituted alkoxyl group, replace or unsubstituted aryl, replace or unsubstituted aryloxy, replace or unsubstituted alkylthio, replace or unsubstituted arylthio; A
21, A
24, A
25, A
28, A
29, A
32, A
33And A
36In at least four each all be to replace or unsubstituted alkoxyl group, replace or unsubstituted aryloxy, replace or unsubstituted alkylthio, replace or unsubstituted arylthio; A
21And A
22, A
22And A
23, A
23And A
24, A
25And A
26, A
26And A
27, A
27And A
28, A
29And A
30, A
30And A
31, A
31And A
32, A
33And A
34, A
34And A
35, A
35And A
36Each to can be respectively forming a ring as intermediary by oxygen and/or sulphur atom; M is a divalent metal atom, replaces trivalent and tetravalent metal atom, or the oxygen metal group.
B wherein
21To B
44In each be respectively hydrogen atom, halogen atom, replacement or unsubstituted alkyl replace or unsubstituted alkoxyl group, replace or unsubstituted aryl, replace or unsubstituted aryloxy, replace or unsubstituted alkylthio, replace or unsubstituted arylthio; B
22And B
23, B
23And B
24, B
24And B
25, B
28And B
29, B
29And B
30, B
30And B
31, B
34And B
35, B
35And B
36, B
36And B
37, B
40And B
41, B
41And B
42, B
42And B
43Each to can be respectively forming ring as intermediary by oxygen and/or sulphur atom; M is a bivalent atom, the trivalent of replacement or tetravalent metal atom, or oxygen metal group.
8. as the desired covering material that is used for plant-growth control in the claim 7, wherein all A
21, A
24, A
25, A
28, A
29, A
32, A
33And A
36All be to replace or unsubstituted alkoxy grp.
9. as the desired covering material that is used for plant-growth control in the claim 7, wherein all B
21, B
26, B
27, B
32, B
33, B
38, B
39, B
44It all is hydrogen atom.
10. as one of any described covering material that is used for plant-growth control of claim 7 to 9, wherein M is Cu, Pd, AlCl, TiO or VO.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5843995 | 1995-03-17 | ||
| JP5843695 | 1995-03-17 | ||
| JP058437/95 | 1995-03-17 | ||
| JP058439/95 | 1995-03-17 | ||
| JP058436/95 | 1995-03-17 | ||
| JP5843795 | 1995-03-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1143654A true CN1143654A (en) | 1997-02-26 |
| CN1082977C CN1082977C (en) | 2002-04-17 |
Family
ID=27296585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96108055A Expired - Lifetime CN1082977C (en) | 1995-03-17 | 1996-03-16 | Covering material for plant growth control |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5953857A (en) |
| EP (1) | EP0732049B1 (en) |
| KR (1) | KR100188444B1 (en) |
| CN (1) | CN1082977C (en) |
| DE (1) | DE69600274T2 (en) |
| ES (1) | ES2116796T3 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100518495C (en) * | 1999-04-30 | 2009-07-29 | 哈伊特卡尔查株式会社 | Cylindrical article for use in controlling growth of tree and method for controlling growth of tree |
| CN1777359B (en) * | 2003-03-06 | 2010-04-28 | 西北大学 | Plant protection covering |
| CN101479326B (en) * | 2006-06-22 | 2011-11-16 | 西巴控股有限公司 | Process for enhancing plant growth |
| CN107455128A (en) * | 2017-08-25 | 2017-12-12 | 兰州大学 | Top method is gone in a kind of sunshade increased production for pea MZ 1 |
| CN108003172A (en) * | 2017-12-12 | 2018-05-08 | 深圳市华星光电技术有限公司 | A kind of green photoresist and its preparation method and application |
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| GB9613476D0 (en) * | 1996-06-27 | 1996-08-28 | British Polythene Ltd | Improvements in or relating to films and/or coatings |
| US6622428B2 (en) * | 2000-02-14 | 2003-09-23 | II Locke White | Method for containing organic debris |
| WO2002019800A2 (en) * | 2000-09-08 | 2002-03-14 | Polysack Plastic Industries (R.A.C.S.) Ltd. | New technology for improving the utilization of sunlight by plants |
| US20040020114A1 (en) * | 2002-07-23 | 2004-02-05 | Bki Holding Corporation | Cellulose support for seed |
| US7470315B2 (en) * | 2005-07-05 | 2008-12-30 | Silverbrook Research Pty Ltd | Red-shifted water dispersible napthalocyanine dyes |
| GR20050100476A (en) * | 2005-09-19 | 2007-04-25 | Πλαστικα Κρητης Αβεε | Machine direction oriented mulching film |
| EP1844656A1 (en) | 2006-04-12 | 2007-10-17 | Ciba Specialty Chemicals Holding Inc. | Use of nanoparticles for increasing the Red to Far Red-ratio |
| BRPI0821058A2 (en) * | 2008-02-08 | 2015-06-16 | Sree Ramcides Chemicals Pvt Ltd | Product to improve photosynthesis |
| WO2009120704A2 (en) * | 2008-03-24 | 2009-10-01 | Plantra, Inc. | A spectrally selective grow tube |
| US8307580B2 (en) * | 2008-03-24 | 2012-11-13 | Plantra, Inc. | Spectrally selective grow tube |
| US8226757B2 (en) * | 2009-10-22 | 2012-07-24 | Hewlett-Packard Development Company, L.P. | Phthalocyanine dye and ink containing the same |
| JP5490560B2 (en) * | 2010-02-16 | 2014-05-14 | 富士フイルム株式会社 | Light guide film and plant growing method using the light guide film |
| CA2884418C (en) * | 2012-09-12 | 2022-06-14 | Extenday Ip Limited | Netting, crop cover, and ground cover materials |
| US9204598B2 (en) | 2013-05-27 | 2015-12-08 | Saudi Basic Indsutries Corporation | Solar energy funneling using thermoplastics for agricultural applications |
| HUE053124T2 (en) | 2013-12-31 | 2021-06-28 | Opti Harvest Inc | Harvesting, transmission, spectral modification and delivery of sunlight to shaded areas of plants |
| WO2016084008A1 (en) | 2014-11-25 | 2016-06-02 | Sabic Global Technologies B.V. | Method and device for heating a surface |
| KR101850490B1 (en) | 2014-11-25 | 2018-04-19 | 사빅 글로벌 테크놀러지스 비.브이. | Method and article for emitting radiation from a surface |
| USD1028646S1 (en) | 2021-04-30 | 2024-05-28 | Opti-Harvest, Inc. | Canopy unit for light harvesting |
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| US2687939A (en) * | 1954-08-31 | Organic compounds useful as dye | ||
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| US3291746A (en) * | 1963-08-26 | 1966-12-13 | American Cyanamid Co | Metal phthalocyanines as infrared absorbers |
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| US3911620A (en) * | 1968-02-14 | 1975-10-14 | Montedison Spa | Materials with a specific photo-selectivity based on synthetic thermoplastic polymers and their use in the agricultural field |
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-
1996
- 1996-03-08 DE DE69600274T patent/DE69600274T2/en not_active Expired - Lifetime
- 1996-03-08 ES ES96103632T patent/ES2116796T3/en not_active Expired - Lifetime
- 1996-03-08 EP EP96103632A patent/EP0732049B1/en not_active Expired - Lifetime
- 1996-03-15 KR KR1019960006939A patent/KR100188444B1/en not_active IP Right Cessation
- 1996-03-16 CN CN96108055A patent/CN1082977C/en not_active Expired - Lifetime
-
1997
- 1997-07-03 US US08/888,282 patent/US5953857A/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100518495C (en) * | 1999-04-30 | 2009-07-29 | 哈伊特卡尔查株式会社 | Cylindrical article for use in controlling growth of tree and method for controlling growth of tree |
| CN1777359B (en) * | 2003-03-06 | 2010-04-28 | 西北大学 | Plant protection covering |
| CN101479326B (en) * | 2006-06-22 | 2011-11-16 | 西巴控股有限公司 | Process for enhancing plant growth |
| CN107455128A (en) * | 2017-08-25 | 2017-12-12 | 兰州大学 | Top method is gone in a kind of sunshade increased production for pea MZ 1 |
| CN108003172A (en) * | 2017-12-12 | 2018-05-08 | 深圳市华星光电技术有限公司 | A kind of green photoresist and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2116796T3 (en) | 1998-07-16 |
| US5953857A (en) | 1999-09-21 |
| DE69600274T2 (en) | 1998-10-01 |
| KR960033242A (en) | 1996-10-22 |
| EP0732049A1 (en) | 1996-09-18 |
| CN1082977C (en) | 2002-04-17 |
| EP0732049B1 (en) | 1998-05-06 |
| KR100188444B1 (en) | 1999-06-01 |
| DE69600274D1 (en) | 1998-06-10 |
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